Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/0208—Tissues; Wipes; Patches
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8129—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers or esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers, e.g. polyvinylmethylether
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
  • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/10—Preparations for permanently dyeing the hair

Definitions

• the present invention relates to film-like agents for dyeing keratinic fibers, in particular human hair, and to processes for dyeing keratinic fibers using corresponding film-shaped agents.
• Oxidationsfärbemittein comes because of their intense colors and good fastness properties of particular importance.
• Such colorants contain oxidation dye precursors, so-called developer components and coupler components.
• the developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components.
• direct dyes can also be added. These are also called direct pullers. These are dye molecules that attach directly to the hair and do not require an oxidative process to form the color. These dyes include, for example, the henna already known from antiquity for coloring body and hair.
• dyeing or tinting agents which contain direct dyes without the addition of oxidation dyes as the coloring component are the means of choice. Often, a natural color shade can only be obtained if colorants containing various substantive dyes are used.
• Both the oxidation colorants and the colorants which allow temporary dyeing are usually formulated in the form of creams, gels or foams. Also, powdered colorants which are mixed with a suitable liquid before use are known.
• a disadvantage of these known forms of colorants is that in particular the consumers who apply the corresponding products at home, often have difficulties with the exact dosage of the colorant.
• the required amount of colorant depends in particular on the desired intensity of the color and the length of the hair to be dyed. If not the entire contents of a package is needed, the correct amount must be measured cumbersome, such as by weighing or determining the removed volume. Incorrect dosage may result in a staining result that does not meet the user's requirements.
• Object of the present invention was therefore to provide a means for dyeing keratinic fibers available, on the one hand gives a uniform, intense Därbench, and on the other hand present in a compact as possible and can be accurately and easily dosed.
• Film-shaped cosmetics are known and have been used for some time in the area of skin treatment, for example as face masks.
• WO 2004/032859 A2 water-soluble leaflets prepared from a composition containing a water-soluble polymer, polyvinyl alcohol, a moisturizer, and a surfactant or a skin-treating ingredient.
• Corresponding leaflets can be according to WO 2004/032859 A2 versatile use, especially in the field of body care, but also in the field of household cleaning. An application in the field of hair coloring is not described.
• WO 2005/070376 A2 discloses hair styling films that can be prepared by a special process. By dissolving or dispersing a polymer in a liquid carrier medium, a rollable formulation is prepared, which is roll-formed into a film and the liquid carrier medium is finally evaporated. A use in the field of hair coloring is not mentioned.
• a first subject of the present invention are therefore film-shaped agents for dyeing keratinic fibers, in particular human hair, comprising at least one film-forming and / or setting polymer and at least one oxidation dye precursor and / or at least one substantive dye.
• keratinic fibers are understood to mean furs, wool, feathers and, in particular, human hair.
• the film-shaped means for dyeing keratinic fibers can be dosed very easily. Depending on the desired dyeing result and the amount of keratinic fiber to be dyed, only a certain number of film-shaped means (leaflets) must be removed and used.
• a film-shaped agent according to the invention is a solid product with planar, planar geometry.
• the leaflets are preferably sized so that an integer number of leaflets can be applied for each individual requirement. But it is also possible in principle to divide the leaflets. This can for example be done very easily with a pair of scissors or a knife.
• the film-shaped means have a thickness of at most 1 mm, in particular of less than 0.5 mm.
• the length and width of the film-shaped means can be selected within wide limits, with dimensions of between 2 and 20 cm, preferably between 3 and 10 cm, having proved advantageous from a production, packaging and application point of view.
• the film-like means for dyeing keratinous fibers contain at least one film-forming and / or setting polymer.
• the amount of film-forming and / or setting polymer depends on the type of polymer, as well as the other ingredients of the film-shaped agent. In any case, however, the amount must be selected so as to obtain a solid film.
• the film-shaped agent contains the film-forming and / or setting polymer as the sole fixing component
• an amount of 50 to 97% by weight is preferable.
• the film-shaped agent contains the film-forming and / or setting polymer in this case in an amount of 60 to 95 weight percent, most preferably in an amount of 80 to 95 weight percent, each based on the total film-shaped agent.
• film-forming and / or setting polymers may be included. These film-forming and / or setting polymers may be both permanent and temporary cationic, anionic, nonionic or amphoteric. When using at least two film-forming and / or setting polymers, these can of course have different charges. It may be preferred according to the invention for an ionic film-forming and / or setting polymer to be used together with an amphoteric and / or nonionic film-forming and / or setting polymer. The use of at least two oppositely charged film-forming and / or setting polymers is also preferred. In the latter case, a particular embodiment may in turn additionally contain at least one further amphoteric and / or nonionic film-forming and / or setting polymer.
• Film-forming polymers are polymers which leave a continuous film on drying. Such film formers can be used in a wide variety of cosmetic products, such as for example face masks, make-up, hair fixatives, hair sprays, hair gels, hair waxes, hair treatments, shampoos or nail varnishes. Particularly preferred are those polymers which have sufficient solubility in water, alcohol or water / alcohol mixtures. This makes it possible to produce appropriate solutions that can be applied or processed in a simple manner.
• the film-forming polymers may be of synthetic or natural origin.
• Film-forming polymers furthermore include those polymers which, when used in 0.01 to 20% strength by weight aqueous, alcoholic or aqueous-alcoholic solution, are capable of depositing a transparent polymer film.
• the film-forming polymers may be anionic, amphoteric, nonionic, permanent cationic or temporarily cationically charged.
• Suitable synthetic film-forming polymers are homopolymers or copolymers which are composed of at least one of the following monomers: vinylpyrrolidone, vinylcaprolactam, vinyl esters such as vinyl acetate, vinyl alcohol, acrylamide, methacrylamide, alkyl and dialkylacrylamide, alkyl and dialkylmethacrylamide, alkyl acrylate, alkyl methacrylate, Propylene glycol or ethylene glycol, wherein the alkyl groups of these monomers are preferably C 1 - to C 7 alkyl groups, more preferably C 1 - to C 3 alkyl groups.
• Examples include homopolymers of vinylcaprolactam, vinylpyrrolidone or N-vinylformamide.
• Further suitable synthetic film-forming fixing polymers are copolymers of vinyl pyrrolidone and vinyl acetate, terpolymers of vinylpyrrolidone, vinyl acetate and vinyl propionate, polyacrylamides, for example, under the trade designations Akypomine ® P 191 by the company CHEM-Y, Emmerich or Sepigel ® 305 by the company Seppic be distributed; Polyvinyl alcohols, for example, under the be sold by Air Products or Celvol ® from Celanese 523/540 tradenames Elvanol.RTM ® Du Pont Vinol ® as well as polyethylene glycol / polypropylene glycol copolymers, for example, under the trade names Ucon ® of Union Carbide to be expelled.
• Suitable natural film-forming polymers include cellulose derivatives, eg. B. hydroxypropyl cellulose having a molecular weight of 30,000 to 50,000 g / mol, which is sold, for example, under the trade name Nisso SI ® by Lehmann & Voss, Hamburg. Also suitable are polysaccharides which are obtained from starch, for example the polysaccharide with the INCI name pullulan.
• setting polymers are also film-forming polymers.
• Examples of common film-forming, setting polymers are Acrylamide / Ammonium Acrylate Copolymer, Acrylamide / DMAPA Acrylates / Methoxy PEG Methacrylate Copolymer, Acrylamidopropyltrimonium Chloride / Acrylamide Copolymer, Acrylamidopropyltrimonium Chloride / Acrylates Copolymer, Acrylates / Acetoacetoxyethyl Methacrylate Copolymer, Acrylates / Acrylamide Copolymer, Acrylates / Ammonium Methacrylate Copolymer, Acrylates / t-Butyl Acrylamide Copolymer, Acrylates Copolymer, Acrylates / C1-2 Succinates / Hydroxy Acrylates Copolymer, Acrylates / Lauryl Acrylates / Stearyl Acrylates / Ethylamine Oxide Methacrylate Copolymer, Acrylates / Octylacrylamide Copoly
• the film-shaped composition according to the invention contains exclusively water-soluble film-forming and / or setting polymers.
• Film-forming and / or setting polymers selected from polysaccharides, polyvinyl alcohol, polyvinylpyrrolidones and vinylpyrrolidone-vinyl acetate copolymers are particularly preferred, wherein the film-forming and / or setting polymer is most preferably a mixture of polyvinyl alcohol and at least one polymer selected from polysaccharides, Polyvinylpyrrolidonen and vinylpyrrolidone-vinyl acetate copolymers, is.
• the products manufactured are preferably used as polyvinyl alcohols, which are sold by Celanese under the name Celvol ®, for example Celvol ® 540 or Celvol ® 523S.
• Preferred polysaccharides are the breakdown products of starch known under the INCI name Pullulen.
• a preferred polyvinylpyrrolidone is PVP K-30 available from ISP.
• As a vinylpyrrolidone-vinyl acetate copolymers preferably Luviskol ® VA 37 W or PVPNA copolymer 60/40 W NP are used.
• the film-shaped agent for dyeing keratin-containing fibers comprises a mixture of polyvinyl alcohol and at least one polymer selected from polysaccharides, polyvinylpyrrolidones and vinylpyrrolidone-vinyl acetate copolymers
• the weight ratio of polyvinyl alcohol to the further polymer is preferably 1.5: 1 to 30: 1, in particular preferably 2: 1 to 10: 1.
• the film-like agents for dyeing keratinic fibers according to the invention furthermore contain at least one oxidation dye precursor and / or at least one substantive dye.
• Suitable substantive dyes are, for example, nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.
• Preferred substantive Dyestuffs are those under the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, HC Red 1, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds, as well as 1, 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis ( ⁇ -hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- ( ⁇ -hydroxyethyl) -
• Preferred cationic substantive dyes of group (c) are in particular the following compounds:
• the compounds of the formulas (DZ1), (DZ3) and (DZ5) which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic substantive dyes of group (c).
• the cationic direct dyes which are sold under the trademark Arianor ®, according to the invention are also very particularly preferred cationic direct dyes.
• Naturally occurring dyes such as those contained in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, sawnwood, madder root, catechu, sedre and alkano root can also be added in nature.
• the substantive dyes are preferably added in an amount such that the total amount of substantive dye 0.1 to 30 wt .-%, preferably 0.1 to 10 wt .-%, particularly preferably 0.1 to 5 wt .-%, each based on the total film-shaped agent is.
• the film-shaped compositions of the present invention contain at least one of the above substantive dyes, but not an oxidation dye precursor.
• the film-shaped keratin fiber dyeing compositions according to the present invention contain, in addition to or instead of at least one of the above substantive dyes, at least one oxidation dye precursor.
• the film-shaped agent contains at least one developer component and optionally additionally at least one coupler component.
• developer components are usually primary aromatic amines having a further, located in the para or ortho position, free or substituted hydroxy or amino, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used ,
• C 1 - to C 4 -alkyl radicals mentioned as substituents in the developer components are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals.
• C 1 -C 4 -alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group.
• a C 1 - to C 4 -hydroxyalkyl group a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned.
• a 2-hydroxyethyl group is particularly preferred.
• a particularly preferred C 2 to C 4 polyhydroxyalkyl group is the 1,2-dihydroxyethyl group.
• halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred.
• the other terms used are derived according to the invention from the definitions given here.
• nitrogen-containing groups of the formula (E1) are, in particular, the amino groups, C 1 - to C 4 -monoalkylamino groups, C 1 - to C 4 -dialkylamino groups, C 1 - to C 4 -trialkylammonium groups, C 1 - to C 4 -monohydroxyalkylamino groups, Imidazolinium and ammonium.
• Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4 -Amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis ( ⁇ -hydroxyethyl) -p-phenylenediamine, 4-N, N-bis ( ⁇ -hydroxyethyl) amino-2 -methylaniline, 4-N, N-
• Very particular preferred p-phenylenediamine derivatives of the formula (E1) according to the invention are p-phenylenediamine, p-toluenediamine, 2- ( ⁇ -hydroxyethyl) -p-phenylenediamine, 2- ( ⁇ , ⁇ -dihydroxyethyl) -p-phenylenediamine, N- ( 4-amino-3-methylphenyl) -N- [3- (1H -imidazol-1-yl) propyl] amine and N, N-bis ( ⁇ -hydroxyethyl) -p-phenylenediamine.
• developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.
• Preferred binuclear developer components of the formula (E2) are in particular: N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis - ( ⁇ -hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-diethyl-N, N ' bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1,
• binuclear developer components of the formula (E2) are N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, Bis - (2-hydroxy-5-aminophenyl) -methane, 1,3-bis (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4'-aminophenyl) -1,4 diazacycloheptane and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane or one of its physiologically acceptable salts.
• Bis (2-hydroxy-5-aminophenyl) methane is a most preferred dinuclear developing agent of formula (E2).
• Preferred p-aminophenols of the formula (E3) are, in particular, p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- ( ⁇ -hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino 2-aminomethylphenol, 4-amino-2- ( ⁇ -hydroxyethyl-aminomethyl) -phenol, 4-amino-2- ( ⁇ , ⁇ -dihydroxyethyl) -phenol, 4-amino-2-fluorophenol, 4-amino-2 -chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethyl-aminomethyl) -phenol and their physiological
• Particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- ( ⁇ , ⁇ -dihydroxyethyl) phenol and 4-amino-2 - (diethylaminomethyl) -phenol.
• the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.
• the developer component may be selected from heterocyclic developer components such as the pyridine, pyrimidine, pyrazole, pyrazole pyrimidine derivatives and their physiologically acceptable salts.
• Preferred pyridine derivatives are in particular the compounds described in the patents GB 1 026 978 and GB 1 153 196 such as 2,5-diamino-pyridine, 2- (4'-methoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2- ( ⁇ -methoxyethyl) -amino 3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.
• Preferred pyrimidine derivatives are, in particular, the compounds which are known in the German Patent DE 2 359 399 A1 , of the Japanese Laid-Open Patent Publication JP 02019576 A2 , the publication WO 00/38629 A1 or the published patent application WO 96/15765 A1 such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.
• Preferred pyrazole derivatives are in particular the compounds described in the patents DE 3 843 892 . DE 4 133 957 and patent applications WO 94/08969 . WO 94/08970 .
• EP-740 931 and DE 195 43 988 such as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- ( ⁇ -hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3 dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-
• coupler components according to the invention are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxy-3,4-dimethylpyridine, 2 - ( ⁇ 3 - [(2-hydroxyethyl ) amino] -4-methoxy-5-methylphenyl ⁇ amino) ethanol, 2 - ( ⁇ 3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl ⁇ amino) ethanol, 2 - ( ⁇ 3- [ (2-hydroxyethyl) amino] -4,5-dimethylphenyl ⁇ amino) ethanol and 2 - [(3-morpholin
• Both the developer components and the coupler components are preferably added in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the total colorant.
• developer components and coupler components are generally used in approximately molar amounts to each other.
• a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2 , may be included.
• the film-shaped compositions for dyeing keratinic fibers may also contain at least one precursor of a naturally-analogous dye.
• Indoles and indolines which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring, are preferably used as precursors of naturally-analogous dyes. These groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group.
• the compounds of the formula (I) are used in admixture with at least one indole and / or indoline derivative.
• Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.
• N-methyl-5,6-dihydroxyindoline N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5, 6-Dihydroxyindolin.
• Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6- dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.
• N-methyl-5,6-dihydroxyindole N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, and especially the 5,6 -Dihydroxyindol.
• the indoline and indole derivatives can be used in the colorant both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, eg. As the hydrochlorides, sulfates and hydrobromides are used.
• the indole or indoline derivatives are usually used in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.
• the indoline or indole derivative in combination with at least one amino acid or an oligopeptide.
• the amino acid is advantageously an ⁇ -amino acid;
• Very particularly preferred ⁇ -amino acids are arginine, ornithine, lysine, serine and histidine, in particular arginine.
• the stated dye precursors or dyes each represent a uniform compound. Rather, in the colorants according to the invention, due to the production process for the individual dyes, in minor amounts, further components may be included, as far as they do not adversely affect the dyeing result or for other reasons, e.g. toxicological, must be excluded.
• Activated by the film-shaped agent for dyeing keratin fibers an oxidation dye precursor, so preferably those oxidation dye precursors are used which are oxidized by atmospheric oxygen, so that the addition of an oxidizing agent is not necessary.
• pyrimidine derivatives which carry at least two amino substituents are therefore used as the developer component.
• combinations of these pyrimidine derivatives are used with at least one coupler component, as in claim 1 of WO 00/38629 A1 to be discribed.
• the film-shaped agents for dyeing keratin-containing fibers as oxidation dye precursor comprise mixtures of at least one developer component selected from 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-2,5,6-triaminopyrimidine, 2,4,5, 6-tetraaminopyrimidine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-5,6-dihydroxypyrimidine, 4-dimethylamino-2,5,6-tetraminopyrimidine and any mixtures thereof, and at least one coupler component of 1,3-bis (2,4-diaminophenoxypropane), 1,3-bis (2,4-diaminophenylpropane), 2,4-diaminophenoxyethanol, 2,6-bis (2'-hydroxyethylamino) -toluene, 3 -Amino-2-chloro-6-methyl-phenol, 5-amino-4-chloro-2
• the agents according to the invention contain at least one 2-electron oxidoreductase, preferably with the respective specific substrate.
• the film-shaped keratinic dyeing agents of the invention further comprise at least one moisture-emitting substance.
• the moisturizing substance is selected from ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerol, polymethacrylic acid glyceryl ester and theirs mixtures.
• the film-type agent according to the invention particularly preferably contains 1,2-propanediol, 1,3-propanediol or mixtures thereof as the moisturizing substance.
• the film-shaped agent according to the invention contains the moisture-emitting substance in an amount of 1 to 50 wt .-%, preferably from 5 to 20 wt .-%, particularly preferably from 10 to 15 wt .-%, each based on the total film-shaped agent.
• the film-like agents for dyeing keratinic fibers according to the invention may furthermore contain all active ingredients, additives and auxiliaries customary for such preparations, for example buffer substances and complexing agents.
• the agents preferably contain at least one surfactant, with both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle.
• nonionic surfactants there are problems with the film formation and thus with the production of the nonionic surfactants are preferably used in combination with ionic surfactants.
• Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the Molecule and in particular salts of saturated and in particular unsaturated C 8 -C 22 carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.
• Preferred nonionic surfactants are alkylpolyglycosides of the general formula R'O- (Z) X. These connections are identified by the following parameters:
• the alkyl radical R ' contains from 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals.
• Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl.
• the alkyl polyglycosides which can be used according to the invention can contain, for example, only one particular alkyl radical R '.
• these compounds are prepared starting from natural fats and oils or mineral oils.
• the alkyl radicals R ' are mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds.
• Sugar unit Z can be used any mono- or oligosaccharides. Usually, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose.
• Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.
• alkyl polyglycosides which can be used according to the invention contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. Very particular preference is given to alkyl glycosides in which x is 1.1 to 1.4.
• the alkyl glycosides can also serve to improve the fixation of fragrance components on the keratinic fiber.
• the person skilled in the art will therefore prefer to resort to this class of substance as a further ingredient of the colorant in the event that an effect of a perfume oil on the keratin fiber beyond the duration of the treatment is desired.
• alkoxylated homologs of said alkyl polyglycosides can also be used according to the invention. These homologs may contain on average up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.
• zwitterionic surfactants can be used, in particular as cosurfactants.
• Zwitterionic surfactants are those surface-active compounds which carry in the molecule at least one quaternary ammonium group and at least one -COO (-) or -SO 3 (-) group.
• Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and Alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethylhydroxyethylcarboxymethylglycinat.
• a preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.
• ampholytes are understood as meaning those surface-active compounds which, apart from a C 8 -C 18 -alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO 3 H group and are capable of forming internal salts.
• ampholytes are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 carbon atoms in the alkyl group.
• Particularly preferred ampholytes are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C 12-18 acylsarcosine.
• Zwitterionic surfactants and ampholytes together form the group of amphoteric or ampholytic surfactants.
• Suitable cationic surfactants are, in particular, those of the quaternary ammonium compound type, the esterquats and the amidoamines.
• Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g.
• alkyltrimethylammonium chlorides dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g.
• cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride and the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83.
• the long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.
• Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element.
• Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines.
• Such products are marketed under the trade names Stepantex® ®, ® and Dehyquart® Armocare® ®.
• the alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines.
• An inventively particularly suitable compound from this group of substances under the name Tegoamid ® S 18 commercial stearamidopropyl dimethylamine is.
• cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.
• cationic silicone oils such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ® quat 3270 and 3272 (manufacturer: Th Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80.).
• Glucquat ® 100 is, according to INCI nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride”.
• the compounds used as surfactant with alkyl groups may each be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures having different alkyl chain lengths depending on the respective raw material are obtained.
• both products with a "normal” homolog distribution and those with a narrow homolog distribution can be used.
• "normal” homolog distribution are meant mixtures of homologs obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homolog distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alkoxides are used as catalysts. The use of products with narrow homolog distribution is preferred.
• the film-shaped keratin fiber dyeing compositions of the invention contain at least one anionic surfactant or a mixture of anionic surfactant and a cationic, amphoteric and / or nonionic surfactant.
• the amount of surfactant is preferably 0.5 to 20 wt .-%, more preferably 2 to 15 wt .-% and most preferably 3 to 12 wt .-%, each based on the total film-shaped agent for dyeing keratinic fibers.
• Suitable auxiliaries and additives are also care substances to call.
• a silicone oil and / or a silicone gum can be used as a care material.
• Silicone oils or silicone gums which are suitable according to the invention are in particular dialkyl and alkylaryl siloxanes, for example dimethylpolysiloxane and methylphenylpolysiloxane, and also their alkoxylated, quaternized or else anionic derivatives. Preference is given to cyclic and linear polydialkylsiloxanes, their alkoxylated and / or aminated derivatives, dihydroxypolydimethylsiloxanes and polyphenylalkylsiloxanes.
• Silicone oils cause a wide variety of effects. For example, at the same time they influence the dry and wet combability, the grip of dry and wet hair and the shine.
• the term silicone oils is understood by the person skilled in the art as meaning several structures of silicon-organic compounds. These are first dimethiconols and dimethicones, such as the marketed by Dow Corning under the name Dow Corning ® 193 Surfactant PEG-12 dimethicones understood. These may be both linear and branched as well as cyclic or cyclic and branched.
• dimethicone copolyols such as are sold, for example, by the company Dow Corning under the designation Dow Corning ® 5330 Fluid
• amino-functional silicones especially the silicones, which are summarized under the INCI designation Amodimethicone.
• the cationic surfactants described above also have a nourishing effect and can therefore be used as a care substance.
• Nursing polymers are likewise suitable as care substances, and these may at the same time have film-forming and / or setting properties.
• a first group of caring polymers are the cationic polymers.
• Cationic polymers are to be understood as meaning polymers which have a group in the main and / or side chain which may be “temporary” or “permanent” cationic.
• “permanently cationic” refers to those polymers which have a cationic group, irrespective of the pH of the agent. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group.
• Preferred cationic groups are quaternary ammonium groups.
• those polymers in which the quaternary ammonium group is bonded via a C 1-4 hydrocarbon group to a polymer main chain constructed from acrylic acid, methacrylic acid or derivatives thereof have proven to be particularly suitable.
• a particularly suitable homopolymer is, if desired, crosslinked, poly (methacryloyloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium-37.
• the crosslinking can be carried out with the aid of poly olefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyallylpolyglyceryl ethers, or allyl ethers of sugars or sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or glucose.
• Methylenebisacrylamide is a preferred crosslinking agent.
• cationized protein hydrolyzates are to be included in the care cationic polymers, the underlying protein hydrolyzate being derived from the animal, for example from collagen, milk or keratin, from the plant, for example from wheat, maize, rice, potatoes, soya or almonds, from marine life forms, from fish collagen or algae, or biotechnologically derived protein hydrolysates.
• the protein hydrolyzates on which the cationic derivatives according to the invention are based can be obtained from the corresponding proteins by chemical, in particular alkaline or acid hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis.
• cationic protein hydrolyzates are to be understood as meaning quaternized amino acids and mixtures thereof.
• the quaternization of the protein hydrolyzates or amino acids is often carried out using quaternary ammonium salts such as N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) ammonium halides.
• the cationic protein hydrolysates may also be further derivatized.
• the cationic protein hydrolyzates and derivatives according to the invention those listed under the INCI names in the " International Cosmetic Ingredient Dictionary and Handbook ", (seventh edition 1997, The Cosmetic, Toiletry and Fragrance Association 1101 17th Street, NW, Suite 300, Washington, DC 20036-4702 Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Casein, Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Hair Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Rice Protein, Cocodimonium Hydroxypropyl Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Hydroxypropyl Arginine Lauryl / Myristyl Ether H
• polymers which can be used according to the invention are amphoteric polymers.
• At least one vitamin, a provitamin, a vitamin precursor and / or one of their derivatives can furthermore be used.
• vitamins, pro-vitamins and vitamin precursors are preferred, which are usually assigned to groups A, B, C, E, F and H. Particularly preferred are vitamins belonging to the B group or to the vitamin B complex, most preferably vitamin B 5 (pantothenic acid, panthenol and pantolactone).
• At least one plant extract can be used.
• extracts are produced by extraction of the whole plant. However, in individual cases it may also be preferred to prepare the extracts exclusively from flowers and / or leaves of the plant.
• short-chain carboxylic acids may in particular be advantageous.
• Short-chain carboxylic acids and their derivatives in the context of the invention are understood to mean carboxylic acids which may be saturated or unsaturated and / or straight-chain or branched or cyclic and / or aromatic and / or heterocyclic and have a molecular weight of less than 750.
• preference may be given to saturated or unsaturated straight-chain or branched carboxylic acids having a chain length of from 1 to 16 C atoms in the chain, very particular preference being given to those having a chain length of from 1 to 12 C atoms in the chain.
• protein hydrolysates and / or their derivatives wherein the use of protein hydrolysates of plant origin, eg. Soy, almond, pea, potato and wheat protein hydrolysates, is preferred.
• Such products are, for example, under the trademarks Gluadin ® (Cognis), diamine ® (Diamalt) ® (Inolex), Hydrosoy ® (Croda), hydro Lupine ® (Croda), hydro Sesame ® (Croda), Hydro tritium ® (Croda) and Crotein ® (Croda) available.
• protein hydrolysates Although the use of the protein hydrolysates is preferred as such, amino acid mixtures otherwise obtained may be used in their place, if appropriate. Also possible is the use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products. Such products are marketed for example under the names Lamepon ® (Cognis), Lexein ® (Inolex), Crolastin ® (Croda), Crosilk ® (Croda) or Crotein ® (Croda).
• lipids and oil bodies for example vegetable oils, liquid paraffin oils, isoparaffin oils, synthetic hydrocarbons and ester oils, enzymes and pearl extracts are suitable as a care substance.
• auxiliaries and additives can be added.
• UV filters are not subject to any general restrictions with regard to their structure and their physical properties. On the contrary, all UV filters which can be used in the cosmetics sector and whose absorption maximum lies in the UVA (315-400 nm), in the UVB (280-315 nm) or in the UVC ( ⁇ 280 nm) range are suitable. UV filters with an absorption maximum in the UVB range, in particular in the range from about 280 to about 300 nm, are particularly preferred.
• the UV filters preferred according to the invention can be selected, for example, from substituted benzophenones, p-aminobenzoic acid esters, diphenylacrylic acid esters, cinnamic acid esters, salicylic acid esters, benzimidazoles and o-aminobenzoic acid esters.
• An example is here 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt (Benzophenone-4; Uvinul ® MS 40; Uvasorb ® S 5) mentioned.
• thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such.
• Suitable alkalizing agents are, for example, alkali metal or alkaline earth metal hydroxides, ammonium, alkali metal and alkaline earth metal carbonates or bicarbonates, ammonia or organic amines.
• Preferred alkalizing agents are monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methylbutanol and triethanolamine, and alkali and alkaline earth metal carbonates.
• ⁇ -amino acids such as ⁇ -aminocaproic acid or alkaline ⁇ -amino acids, such as lysine, ornithine and arginine as alkalizing agent is possible.
• a particularly preferred ⁇ -amino acid is arginine.
• organic acids for example citric acid, may be added for acidification.
• the film-shaped means according to the invention are therefore treated with a powdery, adhering to the leaflet release agent.
• the release agent used is preferably a hydrophobic powder.
• Suitable release agents are, for example, starch or modified starch, for example modified starches, which are known under the INCI names Aluminum Starch Octenylsuccinate and Corn Starch Modified.
• inorganic release agents such as talc or optionally hydrophobized silica powder are suitable. The release agent is applied, for example, to the finished, dry film-shaped agent.
• the film-like agents for dyeing keratinic fibers according to the invention can be produced easily. It has proven useful, first in a known manner, for example by simple stirring, to prepare a solution or dispersion of the film-forming and / or setting polymer in an aqueous solvent and the solution or dispersion, the oxidation dye precursors and / or substantive dyes and the desired auxiliaries and additives admit. It may be advantageous to heat the solution or dispersion during the addition of the individual ingredients.
• aqueous solvent is water or a mixture of water and a C 1 -C 4 -alcohol, in particular ethanol.
• Particularly preferred aqueous solvents are water or a mixture of water and a maximum of 30 wt .-% C 1 -C 4 alcohol, based on the solvent mixture.
• this can be converted, for example, by simple pouring onto a flat surface, by spreading or rolling in a flat shape. Meanwhile or subsequently, the aqueous solvent is evaporated. This can be done by simple storage at room temperature. Preferably, however, the drying takes place at elevated temperature, for example in an oven or by supplying heated air.
• the production process can also be carried out under protective gas, for example nitrogen or argon.
• the finished sheet-shaped agent may be finally cut and packed into the desired size, if necessary.
• the desired number of flakes is first removed from the packaging.
• the agent may then be moistened or completely dissolved or dispersed in water or even an oxidizing agent-containing aqueous solution and then applied to the keratinic fibers to be treated. But it is also possible to apply the leaflets directly to the moistened keratinic fibers, optionally there to spray with water and incorporated into the fibers.
• a second subject of the invention is therefore a process for dyeing keratinic fibers, in particular human hair, wherein a film-shaped agent according to the invention moistened with water, then applied to the keratinic fibers and rinsed again after a contact time or washed out with a shampoo.
• Another object of the invention is a process for dyeing keratinous fibers, especially human hair, wherein the keratinischen moistened fibers, the film-shaped agent according to the invention applied to the moistened keratinic fibers and rinsed again after a contact time or washed out with a shampoo.
• the agent according to the invention can easily be uniformly distributed on the keratinic fiber to be dyed, without undesirable clumping or sticking occurring.
• the actual hair dye is expediently only immediately before use prepared by mixing a preparation of an oxidizing agent with the film-shaped agent.
• the resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6 to 12.
• the pH values given in this document are to be understood as the pH values at 25 ° C.
• Particularly preferred is the use of the hair dye in a weakly alkaline medium.
• the application temperatures can range between 15 and 40 ° C. After a contact time of 5 to 45 minutes, the hair dye is removed by rinsing of the hair to be dyed.
• the oxidizing agents are usually used in an amount of 0.01 to 6 wt .-%, based on the finished application agent.
• a preferred oxidizing agent for human hair is H 2 O 2 .
• Mixtures of several oxidizing agents, such as a combination of hydrogen peroxide and peroxodisulfates of the alkali and alkaline earth metals or from iodide ion sources, such as alkali metal iodides and hydrogen peroxide or the aforementioned peroxodisulfates, can be used.
• the oxidizing agent or the oxidizing agent combination can be used according to the invention in conjunction with oxidation catalysts in the hair dye.
• Oxidation catalysts are, for example, metal salts, metal chelate complexes or metal oxides, which allow a slight change between two oxidation states of the metal ions. Examples are salts, chelate complexes or oxides of iron, ruthenium, manganese and copper.
• Other possible oxidation catalysts are enzymes. Examples of suitable enzymes are peroxidases, which can markedly increase the effect of small amounts of hydrogen peroxide.
• enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the aid of atmospheric oxygen, such as, for example, the laccases, or generate small amounts of hydrogen peroxide in situ and thus biocatalytically activate the oxidation of the dye precursors.
• the film-shaped composition according to the invention can also be applied to the hair without prior mixing with the oxidation component.
• the film-shaped agent can be moistened, for example, with water and applied to the hair or incorporated directly into damp hair. After an exposure time of 20 to 30 minutes then - optionally after an intermediate rinse - the oxidation component can be applied. After a further period of exposure of 10 to 20 minutes, then rinsed and nachshampooniert if desired.
• the corresponding agent is adjusted to a pH of about 4 to 7.
• an air oxidation is initially desired, wherein the applied agent preferably has a pH of 7 to 10.
• the use of acidified peroxydisulfate solutions may be preferred as the oxidizing agent.

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